Apparatus and process for hydrogenations

ABSTRACT

An apparatus and process for treating a complex mixture of hydrocarbons containing undesirable olefinic compounds to remove the mono olefins and diolefins in two stages and separate a desirable key component from the mixture, by first treating the key component in a reactive distillation column under mild conditions to hydrogenate diolefins then separating the diolefin-depleted key component and any lighter materials from the heavier components and sending the diolefin-depleted key component and lighter materials to a second reactive distillation column where the lights are removed overhead and the diolefin-depleted key component is hydrogenated under more severe conditions to remove the mono olefins.

BACKGROUND OF THE INVENTION

[0001] 1. Field of the Invention

[0002] The present invention relates to an apparatus and process for improving the flexibility of operation of reactive distillation hydrogenation processes.

[0003] 2. Related Art

[0004] The use of catalysts in a distillation column to concurrently carry out chemical reactions and separate the reaction products has been practiced for some time. Surprisingly, this use of a catalytic distillation column reactor lends itself particularly well for hydrogenations. See for example, U.S. Pat. Nos. 5,595,634; 5,599,997; 5,628,880; 5,773,670 and European Patent No. 0556025 B1. The combination is useful because the reactants in the liquid phase are quickly separated from the reaction products due to boiling point differences by fractional distillation. Thus further reaction is suppressed.

[0005] Several different arrangements have been disclosed to achieve the desired result. For example, British Patents 2,096,603 and 2,096,604 disclose placing the catalyst on conventional trays within a distillation column. A series of U.S. patents, including those listed above and more, particularly U.S. Pat. Nos. 4,443,559 and 4,215,011 disclose using the catalyst as part of the packing in a packed distillation column. The use of multiple beds in a reaction distillation tower is also known and illustrated, for example, in U.S. Pat. Nos. 4,950,834; 5,321,163; and 5,595,634.

[0006] In reactive distillations, such as catalytic distillation, as in any other distillation, there is no rigid cut off between the components. Reactions carried on in specified portions of the column using some constituents may leave undone other desirable treatment of other portions of the column constituents.

[0007] For example, mixed refinery streams often contain a broad spectrum of olefinic compounds. This is especially true of products from either catalytic cracking or thermal cracking processes (pyrolysis gas). These unsaturated compounds comprise ethylene, acetylene, propylene, propadiene, methyl acetylene, butenes, butadiene, amylenes, hexenes, etc. Many of these compounds are valuable especially as feed stocks for chemical products. Olefins having more than one double bond and the acetylenic compounds (having a triple bond) have lesser uses and are detrimental to many of the chemical processes in which the single double bond compounds are used, for example, polymerization. Sulfur and nitrogen compounds, among others, are frequently desirably removed also and they may be effectively removed from a portion of the column constituents, but because of different boiling points for other portions of the column constituents and the contaminants therein, not all of the contaminants may be removed.

[0008] Generally it is more difficult to remove both dienes and olefins than dienes alone. Diene-rich streams will hydrogenate at a higher volumetric rate under milder conditions than will a diene depleted olefinic stream. Sulfur in the several hundred ppm range is not uncommon for some feeds. Palladium hydrogenation catalysts are not able to handle such high sulfur levels, however, double-digit diene levels often present in these feeds overwhelm the sulfur impurities in their mutual competition for catalyst sites thereby providing reasonable rates notwithstanding.

[0009] In hydrotreating streams with high concentrations of dienes present (above 1000 ppm), there is a need to refrain from using high temperatures to avoid oligomerization. Generally, temperatures in the area of 170° F. or above are avoided. Such operating restraints create conditions which are unfavorable for exhaustive olefin conversion in the same unit in which the diene is eliminated.

[0010] The present invention provides apparatus and process to address the reactive distillation hydrogenation of feed streams having concentrations of both mono and di-olefins.

SUMMARY OF THE INVENTION

[0011] The present invention includes an apparatus for conducting reactive distillations comprising a first distillation column, a first primary catalyst bed for carrying out a hydrogenation of unsaturated compounds comprising diolefins, said first primary catalyst bed being positioned in said distillation column to provide a first reaction zone for diolefins in said first distillation column, and optionally, a first secondary catalyst bed above said first primary catalyst bed, said first secondary catalyst bed to provide a second reaction zone for diolefins remaining in said first distillation column after said first reaction zone, a first mixed saturated/unsaturated compound feed entry below said first primary bed, a hydrogen feed below said primary bed, a bottoms line and an overhead line connecting to a second distillation column comprising a second primary catalyst bed for carrying out hydrogenation of unsaturated compounds comprising mono olefins from said first distillation column, said second primary catalyst bed being positioned in said distillation column to provide a first reaction zone for unsaturated compounds in said second distillation column, and optionally, a second secondary catalyst bed below said second primary bed, said second secondary catalyst bed to provide a second reaction zone for mono olefins remaining in the second distillation column after said first reaction zone, said overhead line from said first distillation column connecting to said second distillation column above said second primary catalyst bed and a hydrogen feed below said second primary bed.

[0012] The process carried out in the apparatus is also part of the present invention.

[0013] There may be distillation structures or trays between the primary and secondary beds. Hydrogenation reactions liberate a significant heat of reaction (on the order of 50,000 or greater BTU/lb mole H₂ consumed). This released heat adds to vapor load in the column. Optionally, side condensers may be used to keep the uniformity of the vapor profile in the column within desired ranges. A secondary catalyst bed may be positioned in the distillation column, above or below the primary bed as heretofore described, to allow lighter or heavier boiling components to be exposed to additional catalyst and be purified or treated further.

[0014] The term “reactive distillation” is used to describe the concurrent reaction and fractionation in a column. For the purposes of the present invention, the term “catalytic distillation” includes reactive distillation and any other process of concurrent reaction and fractional distillation in a column regardless of the designation applied thereto.

[0015] The catalyst beds as used in the present invention may be described as fixed, meaning positioned in a fixed area of the column and include expanded beds and ebulating beds of catalysts. The catalysts in the beds may all be the same or different so long as they carry out the function of hydrogenation as described. Catalysts prepared as distillation structures are particularly useful in the present invention.

BRIEF DESCRIPTION OF THE DRAWING

[0016] The FIGURE is a simplified process flow diagram of one embodiment of the invention.

DETAILED DESCRIPTION OF THE INVENTION

[0017] The present invention is particularly useful for removal of mono olefins and diolefins from cracked gas streams. Thermally cracked gas streams have a particularly wide range of carbon numbers and compound types. Normally, compounds in one carbon number range (such as C₄'s in a C₄/C₅ splitter) will function as the light key grouping in the column. Thus compounds one carbon number greater (such as C₅'s in a C₄/C₅ splitter) will serve as the heavy key grouping for the column.

[0018] Hydrogenation is the reaction of hydrogen with a carbon-carbon multiple bond to “saturate” or partially saturate the compound. This reaction has long been known and is usually done at super atmospheric pressures and moderate temperatures using a large excess of hydrogen over a metal catalyst. Among the metals known to catalyze the hydrogenation reaction are platinum, rhenium, cobalt, molybdenum, nickel, tungsten and palladium. Generally, commercial forms of catalysts use supported oxides of these metals. The oxide is reduced to the active form either prior to use with a reducing agent or during use by the hydrogen in the feed. These metals also catalyze other reactions, most notably dehydrogenation at elevated temperatures. Additionally, they can promote the reaction of olefinic compounds with themselves or other olefins to produce dimers or oligomers as residence time is increased.

[0019] Selective hydrogenation of hydrocarbon compounds has been known for quite some time. Peterson et al in “The Selective Hydrogenation of Pyrolysis Gasoline,” presented to the Petroleum Division of the American Chemical Society in September of 1962, discusses the selective hydrogenation of C₄ and higher diolefins. Boitiaux et al in “Newest Hydrogenation Catalyst”, Hydrocarbon Processing, March 1985, presents a general overview of various uses of hydrogenation catalysts.

FIRST COLUMN

[0020] The first column is operated with the catalyst located above the hydrocarbon feed. It is operated under conditions to reduce only dienes by hydrogenation. The column is operated to move a key component, for example C₅, upward into the primary and any secondary beds under conditions of pressure and temperature to hydrogenate only the dienes, e.g., 150° F. to a top temperature of 170-200° F. at 10 to 75 psig. The exact upper temperature will depend on the diene makeup and other unsaturates such as the acetylenes and the stability of the particular mix of unsaturates to oligomerization.

[0021] The upflow of the key component operates the paradigm shift that keeps the catalyst clean and inhibits coking of the dienes. The faster reaction rates of the dienes compared to the mono olefins in hydrogenation allow short superficial vapor phase contact times in the range of 20-60 seconds.

[0022] The heaviest carbon-range number that is directed upward serves as the light-key carbon range for the column. Compounds of lower carbon number than this behave as the “lighter than light keys” of the system. These lighter compounds tend to equilibrate more into vapor than into liquid which makes reaction for the dienes in that carbon group much more difficult. However, use of a secondary reaction zone with catalyst (above at a lower temperature that the primary bed) allows the concentration of this lower carbon number fraction. Thus, the combined primary bed and the optional upper secondary bed together handle a wider boiling range than would otherwise be achievable.

SECOND COLUMN

[0023] The second column revives the diene depleted overhead from the first column and feeds it above the primary and any optional secondary beds where it is hydrogenated in the reactive distillation mode. In the near absence of dienes e.g. <0.1 wt %, higher temperatures in the range of 200-325° F. are used at pressures in the range of 60-150 psig. Mono olefins-only systems tend to have less favorable hydrogen uptake than diene-rich streams. The superficial vapor phase contact time even under the more severe conditions is 50-90 second range. Note that the key component carbon numbers in the second column may be coincident with or separate from the key component carbon numbers in the first column depending on the objectives of the operation.

[0024] The key component builds up in the column liquid and favors the reaction on the key component. In contrast the heavier carbon-range fraction thins out in the downflowing liquid. However, inclusion of a bottoms secondary catalyst bed (which is lower in the column where the higher temperature causes more boil up of the heavies) can be used to concentrate the heaviest carbon-number range species and react the heavier olefins out more effectively also. As in any distillation there is a temperature gradient within the distillation column reactor. The temperature at the lower end of the column contains higher boiling material and thus is at a higher temperature than the upper end of the column.

[0025] The result of the operation of the process in the distillation column reactor is that lower hydrogen partial pressures (and thus lower total pressures) may be used.

[0026] It is believed that the present distillation column reaction is a benefit first, because the reaction is occurring concurrently with distillation and the initial reaction products and other stream components are removed from the reaction zone(s) as quickly as possible reducing the likelihood of side reactions. Second, because all the components are boiling, the temperature of reaction is controlled by the boiling point of the mixture at the system pressure. The heat of reaction simply creates more boil up, but no increase in temperature at a given pressure. As a result, a great deal of control over the rate of reaction and distribution of products can be achieved by regulating the system pressure. A further benefit that this reaction may gain from distillation column reactions is the washing effect, particularly in the downflow operation of the second column that the internal reflux provides to the catalyst thereby reducing polymer build up and coking.

[0027] Referring now to the FIGURE, a process flow diagram for the removal of unsaturates, primarily mono- and di-olefins from a full range pyrolysis gas. Such items as reboilers, compressors, pumps and the like have been omitted but their normal utilization is readily apparent to those in the art.

[0028] The feed, a pyrolysis gas as described in TABLE 1, enters the first column 10 via line 12. TABLE 1 Component Wt % BD/C4Acetylene 0.2 Butylenes 0.1 Butanes 0.0 C5 Saturates 1.0 C5 Olefins 4.2 C5 Diolefins 13.0 C6 Saturates 2.7 C6 Olefins 2.3 C6 Diolefins 7.0 C7 Saturates 1.5 C7 Olefins 1.1 C7 Diolefins 3.4 C8 Saturates 0.5 C8 Olefins 0.4 C8 Diolefins 1.2 Benzene 18.7 Toluene 17.4 EthylBenzene 2.1 Xylenes 7.6 Styrene 2.6 Heavier 12.9 Total 100.0

[0029] In this illustration the tower 10 is operated under conditions to take the C₆ fraction upward (bottoms −394° F. top −212° F. at 60 psig.) The C₇ and heavier carbon atom components are removed via line 34 for other processing. The C₆ fraction contains some C₇ and heavier but is comprised of predominantly C₆ and lighter carbon number components.

[0030] C₆ components contain principally alkanes, benzene, 5 to 12% mono olefins and 15 to 35% dienes. Similarly, the lighter components contain a wide distribution of species including dienes and mono olefins. Hydrogen is added via line 14 at a rate to provide an excess stoichiometric amount to the dienes present in the C₆ and higher fraction. In bed 16 a hydrogenation catalyst is provided in the form of distillation structure. Under the conditions of temperature and pressure described there is both a vapor and liquid phase comprised principally of the C₆ components and as a result the C₆ dienes are substantially eliminated.

[0031] The higher components under these conditions are principally vaporous in bed 16. However, the temperature in bed 18, also a hydrogenation catalyst as a distillation structure, is lower because of temperature gradient in the column. The secondary bed 18 allows the lower boiling components to undergo the same type of two phase contact as the C₆ fraction in bed 16 thereby allowing a concentration of this higher portion with the dienes substantially eliminated. A side draw 44 is used to remove a portion of the lights diene-depleted concentrate and diene-depleted C₆ into collector 40. A portion of the collected material can be returned via line 42 (dotted line) to the column 10 to maintain the vapor load on the column. Otherwise the material from side draw 44 is fed to the second column 48 via line 46.

[0032] An overhead 20 also containing mostly diene-depleted C₅, C₆ and lighter material goes through condenser 22 into collector 24. The non-condensibles are removed for recycle to the hydrogen feed 14 or for disposal via line 26. A portion of the condensed material is returned as reflux 36 to column 10 and the remainder fed via 38 to line 46 into column 48.

[0033] The feed from column 10 is characterized as having almost all of the diene and greater unsaturates (acetylenes) removed by hydrogenation with little formation of oligomers. The olefins are substantially untouched because of the restricted operating temperature.

[0034] In column 48 the operating conditions are more severe in order to hydrogenate the mono olefins (bottoms −338° F., top −251° F. at 100 psig). The feed enters above primary catalyst bed 50 which is a hydrogenation catalyst prepared as a distillation structure. Again, the conditions are such that the key component, the C₆ constituents, is moved downward. The lighter components, primarily C₅+, exit via overhead line 54 through condenser 52 into collector 58. The non-condensibles are removed either for disposal via line 56 or recycle via line 60 to hydrogen feed 62. A small portion of the liquid in collector 58 is removed via line 78 and the remainder returned via line 76 to column 48 as reflux.

[0035] A collector 66 is located on side draw 64 which removes hydrogenated product via line 74. A portion may be returned via line 68 to control the vapor load on the column. Alternatively the side draw stream 64 may be recovered as a vapor (elimination of the collector 66), which, although it will result in an energy penalty, will provide other benefits, namely (a) further retention of the heavy olefins in the secondary bed 72 and (b) a greater increase in the temperature of bed 72 relative to the primary bed 50, both of which enhance the performance of the secondary bed.

[0036] Secondary bed 72 contains a hydrogenation catalyst as a distillation structure and any heavier fraction remaining is concentrated and given a polishing hydrogenation and recovered via line 70 for combination with the side draw stream 74 into product stream 80.

[0037] Table 2 shows the temperature profile and distribution of the materials in the column 10. The conditions in the secondary catalyst bed 18 (corresponds to trays 4-16) and the primary bed 16 (corresponds to trays 17-30) are represented by the blocked out areas. The other trays are denoted by number. Tray 48 is the reboiler. TABLE 2 PRESS- LI- PRO- TEMP URE QUID VAPOR FEED DUCT TRAY ° F. PSIA LBM/H LBM/H LBM/H LBM/H 1C 101.4 74.7 3510 290.6 vap. 140.2 liq. 2 211.6 74.7 4912 3940 3 215.8 4902 5343 BED 217.7 75.1 4851 5332 18 219.5 75.3 4794 5282 221.3 75.5 4730 5225 223.3 75.7 4658 5161 225.6 75.9 4577 5089 228.4 76.1 4485 5008 231.9 76.3 4385 4916 236.0 76.5 4278 4815 240.6 76.7 4170 4709 245.7 76.9 4064 4601 250.8 77.1 3962 4495 255.9 77.3 3863 4392 260.8 77.5 3266 4294 503.8 Liq BED 265.6 77.7 3184 4201 16 269.4 77.9 3113 4118 272.4 78.1 3050 4047 274.6 78.3 2995 3985 276.2 78.5 2945 3930 277.3 78.7 2898 3879 278.1 78.9 2852 3832 278.7 79.1 2808 3787 279.2 79.3 2764 3743 279.7 79.5 2719 3698 280.2 79.7 2672 3653 281.0 79.9 2621 3606 282.2 80.1 2563 3555 284.3 80.3 2489 3497 31 288.1 80.5 2376 3423 32 296.2 80.7 3532 3311 1206.2 liq.  237.0 vap. 33 310.2 80.9 3645 3023 34 315.3 81.1 3648 3136 35 319.7 81.3 3645 3139 36 324.1 81.5 3639 3136 37 328.7 81.7 3632 3131 38 333.6 81.9 3626 3124 39 338.7 82.1 3621 3117 40 343.8 82.3 3618 3112 41 348.7 82.5 3616 3110 42 353.2 82.7 3613 3108 43 357.5 82.9 3608 3105 44 361.6 83.1 3597 3099 45 366.1 83.3 3575 3088 46 371.6 83.5 3532 3066 47 379.8 83.7 3450 3023 48R 393.5 83.9 2941 508.7 liq.

[0038] Table 3 shows the temperature profile and distribution of materials in column 48. The conditions in the secondary catalyst bed 72 (corresponds to trays 38-46) and the primary bed 50 (corresponds to trays 19-31) are represented by the blocked out areas. The other trays are denoted by number. Tray 49 is the reboiler. TABLE 3 TEMP PRESSURE LIQUID VAPOR FEED PRODUCT TRAY ° F. PSIA LBM/H LBM/H LBM/H LBM/H 1C 131.2 114.7 1504 134.1 vap. 208.7 Liq. 2 251.1 114.7 2247 1846 3 255.4 114.9 2268 2590 4 257.3 115.1 2265 2611 5 259.0 115.3 2258 2607 6 260.6 115.5 2250 2601 7 262.4 115.7 2240 2593 8 264.3 115.9 2228 2583 9 266.5 116.1 2214 2570 10 268.7 116.3 2198 2556 11 271.2 116.5 2182 2541 12 273.8 116.7 2165 2525 13 276.4 116.9 2149 2508 14 279.1 117.1 2132 2492 15 281.8 117.3 2116 2475 16 284.4 117.5 2099 2458 17 287.0 117.7 2974 2442 643.9 liq. 18 289.9 117.9 2936 2673 BED 292.0 118.1 2891 2635 50 293.9 118.3 2846 2590 295.6 118.5 2802 2545 297.2 118.7 2758 2501 298.6 118.9 2715 2457 299.8 119.1 2671 2413 301.0 119.3 2628 2370 302.1 119.5 2585 2327 303.1 119.7 2541 2284 304.0 119.9 2497 2240 305.0 120.1 2452 2196 306.0 120.3 2406 2151 307.2 120.5 2358 2105 32 308.6 120.7 1981 2056 326.2 liq. BED 310.2 120.9 1968 2006 72 312.2 121.1 1955 1993 314.4 121.3 1941 1980 316.7 121.5 1928 1966 319.1 121.7 1916 1953 321.4 121.9 1906 1941 323.5 122.1 1899 1931 325.4 122.3 1894 1924 326.9 122.5 1890 1919 328.1 122.7 1888 1915 329.0 122.9 1887 1913 329.7 123.1 1886 1912 330.2 123.3 1886 1911 330.7 123.5 1886 1911 47 331.0 123.7 1876 1911 108.5 vap. 48 338.0 123.9 1925 1792 49R 338.3 124.1 1841 83.4 liq. 

The invention claimed is:
 1. An apparatus for conducting reactive distillations comprising a first distillation column, a first primary catalyst bed for carrying out a hydrogenation of unsaturated compounds comprising diolefins, said first primary catalyst bed being positioned in said distillation column to provide a first reaction zone for diolefins in said first distillation column, a first mixed saturated/unsaturated compound feed entry below said first primary bed, a hydrogen feed below said primary bed, a bottoms line and an overhead line, said overhead line connecting to a second distillation column comprising a second primary catalyst bed for carrying out hydrogenation of unsaturated compounds comprising mono olefins from said first distillation column, said second primary catalyst bed being positioned in said distillation column to provide a first reaction zone for unsaturated compounds in said second distillation column, said overhead line from said first distillation column connecting to said second distillation column above said second primary catalyst bed and a hydrogen feed below said second primary bed.
 2. The apparatus according to claim 1 wherein a first secondary catalyst bed is positioned in said first column above said first primary catalyst bed, said first secondary catalyst bed to provide a second reaction zone for diolefins remaining in said first distillation column after said first reaction zone.
 3. The apparatus according to claim 1 wherein a second secondary catalyst bed is positioned in said second column below said second primary bed, said second secondary catalyst bed to provide a second reaction zone for mono olefins remaining in the second distillation column after said first reaction zone.
 4. The apparatus according to claim 1 wherein a first secondary catalyst bed is positioned in said first column above said first primary catalyst bed, said first secondary catalyst bed to provide a second reaction zone for diolefins remaining in said first distillation column after said first reaction zone and a second secondary catalyst bed is positioned in said second column below said second primary bed, said second secondary catalyst bed to provide a second reaction zone for mono olefins remaining in the second distillation column after said first reaction zone.
 5. The apparatus according to claim 1 wherein a side draw is connected to withdraw a portion of the liquid in said first column into a collector, said collector being connected to said second distillation column above said second primary catalyst bed.
 6. The apparatus according to claim 2 wherein a side draw is connected to withdraw a portion of the compounds in said first column below said first secondary catalyst bed into a collector, said collector being connected to said second column above said second primary catalyst bed.
 7. The apparatus according to claim 1 wherein a side draw is connected to withdraw a portion of the compounds in said second column into a collector, said collector being connected to a product recovery line.
 8. The apparatus according to claim 3 wherein a side draw is connected to withdraw a portion of the liquid in said second column below said second primary catalyst bed into a collector, said collector being connected to a product recovery line.
 9. A process for conducting reactive distillation hydrogenations comprising feeding hydrogen and a stream comprising hydrocarbons in a range of carbon atoms and including mono olefins and diolefins below a first primary reaction zone containing a hydrogenation catalyst under conditions of concurrent reaction and distillation to bring a key component being less than said range of carbon atoms into said first primary reaction zone containing a hydrogenation catalyst, to hydrogenate diolefins, recovering a diolefin-depleted key component stream, separating a stream comprising hydrocarbons of more carbon atoms than said key component, feeding said diolefin-depleted stream above and hydrogen below a second primary reaction zone under conditions of concurrent reaction and distillation to hydrogenate mono olefins and separate hydrocarbons having fewer carbon atoms than said key component and recovering a product comprising said key component and being mono olefin-depleted and diolefin-depleted.
 10. The process according to claim 9 wherein said key component and heavier components from said second primary reaction zone enters into a second secondary reaction zone containing a hydrogenation catalyst under conditions of concurrent reaction and distillation to hydrogenate mono olefins.
 11. The process according to claim 10 wherein a side draw fraction is withdrawn from said second primary reaction zone and a portion of said side draw fraction is returned to said second primary reaction zone.
 12. The process according to claim 10 wherein a side draw fraction is withdrawn from said second primary reaction zone as vapor.
 13. The process according to claim 9 wherein said key component and lighter hydrocarbons from said first primary reaction zone enter into a first secondary reaction zone containing a hydrogenation catalyst under conditions of concurrent reaction and distillation to hydrogenate diolefins.
 14. The process according to claim 13 wherein a side draw fraction is removed from said first secondary reaction zone and a portion of said side draw fraction is returned to said first secondary reaction zone.
 15. The process according to claim 9 wherein after said first primary reaction zone said key component and lighter hydrocarbons enter into a first secondary reaction zone containing a hydrogenation catalyst under conditions of concurrent reaction and distillation to hydrogenate diolefins and after said second primary reaction zone said key component enters into a second secondary reaction zone containing a hydrogenation catalyst under conditions of concurrent reaction and distillation to hydrogenate mono olefins. 